2,5-diferrocenyl-1-phenyl-1H-pyrrole | 1263048-83-4

• 英文名称: 2,5-diferrocenyl-1-phenyl-1H-pyrrole
• 英文别名: 2,5-diferrocenyl-1-phenylpyrrole
• CAS: 1263048-83-4
• 化学式: C₃₀H₂₅Fe₂N
• 分子量: 511.229
• InChiKey: VLDGWYFJRJEXJW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  2,5-diferrocenyl-1-phenyl-1H-pyrrole 在 (n-Bu₄N)(B(C₆F₅)4) 作用下， 以 二氯甲烷 为溶剂， 生成 2,5-diferrocenyl-1-phenyl-1H-pyrrole(1+)
  参考文献：
  名称：

  杂环核心系统中电子离域对2,5-二-和2,3,4,5-四茂铁基噻吩，呋喃和吡咯的电化学通信的影响

  摘要：

  使用Negishi C，C交叉偶联方案合成了一系列2,5-二-和2,3,4,5-四茂铁基取代的噻吩，呋喃和吡咯。通过循环伏安法（CV），方波伏安法（SWV）和原位UV-vis / NIR光谱法研究了这些化合物的电子和电化学性质。讨论了固态的2,5-二茂铁基呋喃和2,3,4,5-四茂铁基-1-甲基-1 H-吡咯的分子结构。二茂铁基可被顺序地氧化，以给出适当的二或四铁二茂铁基取代的杂环分子的两个或四个可逆反应。观测到的ΔE°'值的范围介于186和450 mV之间。NIR测量结果证实了电子通信，因为在相应的单-二茂铁基化合物中发现了间隔电荷转移（IVCT）吸收，在双亲性化合物中也发现了这种吸收。根据罗宾和戴（Robin and Day），除四铁茂铁噻吩（I类系统）外，所有化合物均分类为II类系统。它们显示了ΔE °′和IVCT振荡器强度f之间的线性关系。这可能是有机金属化学中的首次展示。这是可能

  DOI：

  10.1021/ic200926z
• 作为产物：
  描述：

  二茂铁 、 2,5-dibromo-1-phenyl-1H-pyrrole 在 正丁基锂 、 potassium tert-butylate 、 zinc chloride*2(tetrahydrofuran) 、 C₂₄H₅₄Cl₂P₂Pd₂⁽²⁺⁾ 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 13.5h， 生成 2,5-diferrocenyl-1-phenyl-1H-pyrrole
  参考文献：
  名称：

  Molecular Wires using (Oligo)pyrroles as Connecting Units: An Electron Transfer Study

  摘要：

  A series of (oligo)pyrroles featuring redox-active terminal ferrocenyl groups (Fc(2)-((C4H2NPh)-C-c)(n) (4, n = 1; 9, n = 2; 16, n = 3; 20, n = 4)) has been prepared using a Negishi C,C cross-coupling reaction protocol. The bi-, ter-, and quaterpyrrole wire moieties have been built up by C,C cross-coupling reactions of trimethylsilyl-protected pyrrole units in the presence of [Pd(CH2C(CH3)2(P)((C4H9)-C-t)(2))(mu-Cl)](2) as precatalyst. The structural properties of the title compounds were investigated by spectroscopic means and single-crystal X-ray diffraction studies (9, 16, and 20). The influence of the increasing number of N-phenylpyrrole units on the electronic interaction between the iron centers was studied using electrochemistry (cyclic (CV) and square wave voltammetry (SWV)) as well as spectroelectrochemistry (in situ UV/vis/near-IR spectroscopy). With the exception of the diferrocenyl quaterpyrrole 20, the application of [(NBu4)-Bu-n][B(C6F5)(4)] as electrolyte allows the discrete oxidation of the ferrocenyl termini (Delta E degrees' = 450 mV (4), Delta E degrees' = 320 mV (9), Delta E degrees' = 165 mV (16)) in cyclic and square wave voltammograms. However, the iron centers of 20 were oxidized simultaneously, generating dicationic 20(2+). Additionally, one (9) or two (16 and 20) pyrrole-related well-defined reversible one-electron-redox processes were observed. The cyclic voltammetry data reveal that the splitting of the ferrocene-based redox couples, Delta E degrees', decreases with increasing oligopyrrole chain length and, hence, a greater metal-metal distance. The trends in Delta E degrees' with oligopyrrole structure also map to the electronic coupling between the ferrocene moieties, as estimated by spectroelectrochemical UV/vis/near-IR measurements. Despite the fact that there is no direct metal-metal interaction in diferrocenyl quaterpyrrole 20, a large absorption in the near-IR region is observed arising from photoinduced charge transfer from the oligopyrrole backbone to the redox-active ferrocenyl termini. These charge transfer absorptions have also been found in the dicationic oxidation state of the mono-(4), bi- (9), and terpyrroles (16). Within this series of diferrocenyl(oligo)pyrroles this CT band is shifted bathochromically with increasing chain length of the backbone motif.

  DOI：

  10.1021/om4007533

文献信息

• Synthesis of 2,5-diferrocenyl five-membered heterocyclic compounds and their electrochemistry
  作者：Yu-Qiang Hu、Li-Min Han、Ning Zhu、Hai-Long Hong、Rui-Jun Xie

  DOI：10.1080/00958972.2013.841902

  日期：2013.10.10

  A series of 2,5-diferrocenyl substituted five-membered heterocyclic compounds, 2,5-diferrocenyl-1-phenylpyrrole (1), 2,5-diferrocenyl-1-(4-fluorophenyl)-pyrrole (2), 2,5-diferrocenyl-1-(4-ethoxyphenyl)-pyrrole (3), 2,5-diferrocenyl-1-(4-ethylphenyl)-pyrrole (4), 2,5-diferrocenylthiophene (5), and 2,5-diferrocenylfuran (6), were synthesized using one-pot cycloaddition of ferrocenyl alkyne and characterized by elemental analysis, FT-IR, MS, and NMR. The molecular structures of 1, 2, 5, and 6 were determined using single-crystal X-ray diffraction. Electronic communication between two ferrocenyl units of 1-6 was investigated using cyclic voltammetry. These compounds have two well-resolved electrochemically reversible one-electron-transfer processes using [NBu4][PF6] as the supporting electrolyte. The electrochemical studies reveal that electronic communication between two ferrocenyl units depend on the heteroatoms.
• Electronically Intercommunicating Iron Centers in Di- and Tetraferrocenyl Pyrroles
  作者：Alexander Hildebrandt、Dieter Schaarschmidt、Heinrich Lang

  DOI：10.1021/om100914m

  日期：2011.2.14

  Novel 2,5-diferrocenyl-1-phenyl-1H-pyrrole (4) and 2,3,4,5-tetraferrocenyl-1-phenyl-1H-pyrrole (6) have been prepared by a 2- or 4-fold Negishi cross-coupling reaction of 2,5-dibromo-1-phenyl-1H-pyrrole (3) and 2,3,4,5-tetrabromo-1-phenyl-1H-pyrrole (5), respectively, with FcZnCl (2) (Fc = Fe(eta(5)-C5H4)(eta(5)-C5H5)) in the presence of [(Ph3P)(4)Pd] as catalyst. The electronic and structural properties of 4 and 6 were investigated with UV-vis spectroscopy and single-crystal X-ray diffraction (6). Comparison of the appropriate bond distances in the pyrrole core system of 6 demonstrates considerable electron delocalization. Cyclic, square wave, and linear sweep voltammetry as well as in situ MR spectro-electrochemistry highlight the electrochemical properties of both compounds. Molecules 4 and 6 display two (4) or four (6) electrochemically reversible one-electron transfer processes with remarkably high Delta E-1/2 values and reduction potentials of E-0t = -238 and E-0t = 212 mV for 4 (Delta E-1/2 = 450 mV) and E-0t = 280, E-0t = 51, E-0t = 323, and E-0t = 550 mV for 6 (Delta E-1/2 = 322, 2154, and 233 mV) using [NBu4][B(C6F5)(4)] as the supporting electrolyte. The pyrroles could be classified as class II systems according to Robin and Day. Additionally, 4[PF6](n) (n = 1, 2) were synthesized and studied, giving CV responses and NIR spectra identical to those obtained for 4 from electrochemical oxidations.